Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J25/00—Catalysts of the Raney type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols

Definitions

• This invention relates to a novel process for producing aminocarboxylic acid salts useful as starting materials of agricultural chemicals and medicines, chelating agents, food additives, and so on.
• 2,384,817 discloses a process in which potassium glycinate is formed by anhydrously reacting monoethanolamine with potassium hydroxide in the presence of a copper catalyst. In this process, however, according to the present inventors' knowledge, a yield of the glycinate is not good.
• U.S. Pat. No. 3,578,709 discloses a process in which a nitrilotriacetic acid salt is formed by reacting triethanolamine with an alkali hydroxide in the presence of a zinc oxide catalyst. This process is, nevertheless, unsatisfactory in a yield of the nitrilotriacetic acid salt.
• 3,842,081 discloses that potassium iminodiacetate is obtained in a relatively high yield by reacting diethanolamine with potassium hydroxide in the presence of cadmium oxide.
• U.S. Pat. Nos. 3,535,373, 3,578,709 and 3,739,021 disclose that a nitrilotriacetic acid salt is formed by reacting triethanolamine with an alkali hydroxide in the presence of cadmium oxide.
• these processes using cadmium oxide as a catalyst cannot be used at all depending on the use and suffer a problem of waste matters; they cannot become a technology competitive with the Strecker process.
• Main by-products are an oxalic acid salt when producing a glycine salt using monoethanolamine as a starting material, a glycine salt when producing an iminodiacetic acid salt using diethanolamine as a starting material, and an iminodiacetic acid salt and a glycine salt when producing a nitrilotriacetic acid salt using triethanolamine as a starting material. Accordingly, in order to obtain the aminocarboxylic acid with good selectivity, there is a need to exchange the catalyst for a short period of time or to recover the catalyst by a complex purification step.
• the present inventors have made various investigations, in view of the aforesaid problems, on a process in which an aminocarboxylic acid salt is formed by oxidatively dehydrogenating an amino alcohol in the presence of a copper-containing catalyst, and consequently have found that when an aluminum metal and/or an aluminum compound is added to an oxidative dehydrogenation reaction system, it is effective for suppressing formation of by-products. Further extensive investigations have led to completion of this invention.
• reaction in the presence of an alkali metal hydroxide and/or an alkaline earth metal hydroxide, a copper-containing catalyst and water, characterized in that the reaction is carried out by adding an aluminum metal and/or an aluminum compound to the reaction system.
• CH 20 H of the amino alcohol represented by formula (1) is oxidatively dehydrogenated to COOH.
• R 1 and R 2 in formula (1) are hydroxyethyl groups
• CH 2 OH's thereof are also oxidatively dehydrogenated to COOH's; obtaining an aminocarboxylic acid salt containing plural COOH's is also included in this invention.
• Examples of the amino alcohol represented by formula (1) are monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-nonylethanolamine, N-(2-aminoethyl)ethanolamine, N-(3-aminopropyl)ethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-ethyl-N-(2-aminoethyl)ethanolamine, and N-methyl-N-(3-aminopropyl)ethanolamine.
• aminocarboxylic acid salts can be produced.
• the aminocarboxylic acid are glycine, iminodiacetic acid, nitrilotriacetic acid, N-methylglycine, N-ethylglycine, N-isopropylglycine, N-butylglycine, N-nonylglycine, N-(2-aminoethyl)glycine, N-(3-aminopropyl)glycine, N,N-dimethylglycine, N,N-diethylglycine, N,N-dibutylglycine, N-methyliminodiacetic acid, N-ethyliminodiacetic acid, N-isopropyliminodiacetic acid, N-butyliminodiacetic acid, N-ethyl-N-(2-aminoethyl)glycine, and N-methyl-N-(3
• the catalyst used in this invention contain copper as an essential component.
• a copper source metallic copper, copper oxide, copper hydroxide, copper inorganic salts such as copper nitrate, copper sulfate, copper carbonate and copper halides, and copper organic salts such as copper formate, copper acetate, copper propionate and copper lactate are available.
• the form of the catalyst is not particularly limited.
• a catalyst obtained by oxidizing a surface of metallic copper and then reducing it with hydrogen, a catalyt obtained by developing Raney copper with an alkali aqueous solution, and activated copper obtained by thermally decomposing and/or reducing copper formate, copper carbonate, or the like can be used either as such or by supporting same on an alkali-resistant carrier.
• the catalyst When the catalyst is used by supporting it on the alkali-resistant carrier, said catalyst can easily be separated from the reaction mixture after the reaction, with a result that it can easily be recovered and reused advantageously.
• the catalyst which is especially preferable in the aspects of its activity and life are developed Raney copper and a product obtained by supporting copper on zirconium oxide or silicon carbide by coprecipitation or impregnation.
• the amount of the catalyst used is 1 to 70% by weight, preferably 10 to 40% by weight based on the weight of the amino alcohol.
• alkali metal hydroxide or the alkaline earth metal hydroxide used in this invention sodium hydroxide, potassium hydroxide, etc. are especially preferable. They can be used in the form of a flake, a powder, pellets or an aqueous solution; the aqueous solution is preferable from the aspect of handling.
• the amount of the alkali metal hydroxide or the alkaline earth metal hydroxide is equivalent or more, preferably 1.0 to 2.0 equivalents based on the amount of the hydroxyl group of the amino alcohol used in the reaction.
• Examples of the aluminum compound used in this invention are aluminum hydroxide, aluminic acid salts such as sodium aluminate and potassium aluminate, and aluminum halides such as aluminum chloride.
• sodium aluminate or aluminum hydroxide is preferably used.
• the amount of the aluminum metal and/or the aluminum compound is 0.001% by weight or more, as an aluminum atom, based on the weight of the amino alcohol, which is effective for suppressing by-products. Preferable is 0.002 to 0.5% by weight. When said amount exceeds 0.5% by weight, it is economically disadvantageous, though it does not adversely affect the yield of the aminocarboxylic acid salt.
• the catalyst can be separated and recovered from the reaction system and reused in the next reaction.
• a required amount of a non-used catalyst may be added.
• the non-used catalyst contains an aluminum metal and/or an aluminum compound
• the aluminum metal and/or the aluminum compound is deemed an aluminum metal and/or an aluminum compound added to the reaction system according to this invention.
• the process of this invention is carried out in the presence of water.
• the use of water has a merit that the amino alcohol can uniformly be reacted with the alkali metal hydroxide and/or the alkaline earth metal hydroxide, and is inevitable for obtaining the aminocarboxylic acid salt in high yield.
• the amount of water used in the reaction is 10% by weight or more, preferably 50 to 500% by weight based on the weight of the amino alcohol.
• the reaction temperature is usually 220° C. or lower, preferably 120° to 210° C., most preferably 140° to 200° C. in order to prevent thermal decomposition and hydrogenolysis of a carbon-nitrogen bond of the amino alcohol and the resulting aminocarboxylic acid.
• the reaction pressure is preferably as low as possible from the aspect of a reaction rate. It is usually more than the minimum pressure to advance the reaction in a liquid phase, preferably 5 to 50 kg/cm 2 G.
• the reaction can be carried out batchwise, semibatchwise or continuously.
• the aqueous solution of the intended aminocarboxylic acid salt is obtained as a filtrate. It is properly purified as required, thereby obtaining a high-quality amino-carboxylic acid salt as a product.
• the catalyst separated by filtration can be recovered and reused as such in the next reaction. Of course, the recovered catalyst may be used by proper regeneration treatment as required.
• the aluminum metal and/or the aluminum compound is added to the reaction system in oxidatively dehydrogenating the amino alcohol in the presence of the alkali metal hydroxide and/or the alkaline earth metal hydroxide, the copper-containing catalyst and water, with a result that the intended aminocarboxylic acid salt can be produced in high yield with high selectivity.
• the process of this invention can effectively suppress by-products remarkably especially when recovering the catalyst and repeatedly using it in comparison to the conventional processes wherein the aluminum metal or the aluminum compound is not added to the reaction system.
• the recovered catalyst can be circulated and reused without the regenerating treatment in most cases considerably reducing the cost of the catalyst, purification of the intended aminocarboxylic acid salt becomes easy, the amounts of the waste matters are decreased, and the high-quality product can be supplied inexpensively.
• the process of this invention can also be carried out using a copper-containing catalyst recovered from the reaction mixture obtained by the conventional process in which the aluminum metal or the aluminum compound is not added to the reaction system. In this instance, by-products can be suppressed too.
• a 500 ml autoclave was charged with 80 g of diethanolamine, 64 g of sodium hydroxide, 170 g of water, g of developed Raney copper, and 0.13 g (corresponding to 0.054% by weight, as an aluminum atom, based on the weight of the amino alcohol) of sodium aluminate, and the atmosphere inside the autoclave was replaced thrice with a hydrogen gas. Then, the reaction was conducted at a temperature of 170° C. and a pressure of 10 kg/cm 2 G until occurrence of hydrogen was no longer observed. The time required for the reaction (a time that lapsed from the temperature rise to 170° C. to the termination of the reaction - this is the same in the following) was 5 hours.
• a 500 ml autoclave was charged with 80 g of diethanolamine, 64 g of sodium hydroxide, 170 g of water and 8 g of developed Raney copper, and the atmosphere inside the autoclave was replaced thrice with a hydrogen gas. The reaction was then conducted at a temperature of 170° C. and a pressure of 10 kg/cm 2 G until occurrence of hydrogen was no longer observed.
• a 500 ml autoclave was charged with 80 g of diethanolamine, 64 g of sodium hydroxide, 170 g of water, 16 g of developed Raney copper and 0.024 g (corresponding to 0.010% by weight, as an aluminum atom, based on the weight of the amino alcohol) of sodium aluminate, and the atmosphere inside the autoclave was replaced thrice with a hydrogen gas.
• the reaction was then carried out at a reaction temperature of 160° C. and a reaction pressure of 10 kg/cm 2 G until occurrence of hydrogen was no longer observed.
• the time required for the reaction was 5 hours after the temperature was raised to 160° C. After the reaction was over, the reaction solution was taken out and analyzed. As a result, conversion of diethanolamine was 98.5%, selectivity to sodium iminodiacetate was 99.1, and selectivity to by-product sodium glycinate was 0.5%.
• Example 5 was repeated except that sodium aluminate was not used.
• a 500 ml autoclave was charged with 84 g of monoethanolamine, 61 g of sodium hydroxide, 132 g of water and 17 g of developed Raney copper, and the atmosphere inside the autoclave was replaced thrice with a hydrogen gas.
• the reaction was then conducted at a reaction temperature of 160° C. and a reaction pressure of 10 kg/cm 2 G until occurrence of hydrogen was no longer observed.
• the experiment was repeated under the same reaction conditions.
• the reaction time required for the 10th repeated experiment was 5 hours after the temperature rise.
• a 500 ml autoclave was charged with 58 g of triethanolamine, 51 g of sodium hydroxide, 170 g of water, 17 g of developed Raney copper and 0.035 g (corresponding to 0.020% by weight, as an aluminum atom, based on the weight of the amino alcohol) of sodium aluminate, and the atmosphere inside the autoclave was replaced thrice with a hydrogen gas, and the reaction was then conducted at a reaction temperature of 190° C. and a reaction pressure of 10 kg/cm 2 G until occurrence of hydrogen was no longer observed. The time required for the reaction was 7 hours after the temperature was raised to 190° C. After the reaction was over, the reaction solution was taken out and analyzed.
• Example 5 The reaction was conducted as in Example 5 except that sodium aluminate was not used.
• a 500 ml autoclave was charged with 58 g of triethanolamine, 51 g of sodium hydroxide, 170 g of water, and 17 g of developed Raney copper, and the atmosphere inside the autoclave was replaced thrice with a hydrogen gas.
• the reaction was then carried out at a reaction temperature of 190° C. and a reaction pressure of 10 kg/cm 2 G until occurrence of hydrogen was no longer observed.
• the experiment was repeatedly conducted under the same reaction conditions.
• the reaction time required for the 10th repeated experiment was 15 hours after the temperature rise.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=17707441

Family Applications (1)

Country Status (11)

Cited By (9)

Families Citing this family (11)

Citations (7)

Family Cites Families (6)

• 1991
  • 1991-10-21 US US07/861,893 patent/US5220055A/en not_active Expired - Lifetime
  • 1991-10-21 DK DK91917813.7T patent/DK0506973T3/da active
  • 1991-10-21 EP EP91917813A patent/EP0506973B1/de not_active Expired - Lifetime
  • 1991-10-21 CA CA002071999A patent/CA2071999C/en not_active Expired - Lifetime
  • 1991-10-21 JP JP3516543A patent/JP2916256B2/ja not_active Expired - Lifetime
  • 1991-10-21 DE DE69115883T patent/DE69115883T2/de not_active Expired - Lifetime
  • 1991-10-21 WO PCT/JP1991/001440 patent/WO1992006949A1/ja active IP Right Grant
  • 1991-10-21 AU AU87117/91A patent/AU636803B2/en not_active Expired
  • 1991-10-21 ES ES91917813T patent/ES2081497T3/es not_active Expired - Lifetime
  • 1991-10-21 KR KR1019920701507A patent/KR950006892B1/ko not_active IP Right Cessation
  • 1991-10-23 MX MX9101721A patent/MX9101721A/es unknown

Patent Citations (7)

Also Published As

Similar Documents

Legal Events